CATtech-6 Sy mat hoat tinh ctia xtic tac Catalyst deactivation 4 Noi dung 1, Cac nguyén nhan va co ché (Causes and mechanisms) 2. Phuong phap phéng va xt ly (Prevention and treatment methods) 4 1. Cac nguyén nhan va co’ ché (Causes and mechanisms) 4 + Bao vé catalyst khoi mat hogt tinh la mot thieh, thie In trong thiét ké va van hanh hé théng phan ing xiie tée quy mé lén, + 5 nguyén han: ~(1) poisoning (du dc), 2) fouling (tie mghén), (3) thermal degradation (thodi héa nhigt), = (4) loss of catalytic phases by vaporsoid andor sotid- solid reactions (including formation o* volatile compounds) CEhat thot pha hot tinh), = (5) attrition (mai man). + 3nh6m: H6a, eo va Nhigt.Poisoning + Poisoning: strong chemisorption of reactants, products or impurities on catalytic sites, Poisoning Conn ot ping by ite emt ma aie big CO rg ms oma Poisoning StS SSeS] Effeets: ie 1. blocking adsorption/eaction sites 2, modifying its nearest-neighbor meal atoms thereby modifying heir abilities to adsorb andor dissociate reactant melecules 3. Restructuring the surface by the stroagly adsorbed poison, possibly. 4. Causing dramatic changes in catalytic properties, especially for reactions sensitive to surface structure 5. blocking access of adsorbed reactants t cach other 6. preventing ar slowing the surface diffusion of adsorbed reactants,Poisoning + Poisoning Common Poisons Acoting Chem Orga = Tange Grea REMORSE Teshemeinte PA 24 CAFE Mieuercaioenn CON Ae te Tear ma ay et may ‘Geman wae | oy + Interactions of Group VA and VIA elemens with catalytic metal paces depend on the ovidatin sat the emer {ce how many electron pairs are availabe for bonding tnd he degree of shielding by ligands, + Decreasing tency for sulfur species is H,S > SO, > S02 Poisoning rms 3 rms » Poisoning Poisoning + Toxicity ineases with increasing atomic oF satpate a molecular size and clectro-negativity Ease ae a on — = Tima cle Gon a yaa + Toxicity decreases if the poison exhibits the Ninn ce et. tment ha aM tendeney to be gasified by 0, H,O or Hy present ea ei CREO in the reactant stream NSteanatin — Ghdomonlrow” ACOA NK ean dannii ca etenabsmin Heng sseter en cunrenerne ” Semimmentrom rihanna Pann ann anf evvtaes TARAS Couemiawnstla_tyewaaysteate anes Nd Yom rms a rms FaPoisoning a Ifpoisoning of the most active sites eccurs preferentially at low concentrations, the poisoning process is ‘sclective.” If sites of lesser activity are poisoned initially, the poisoning is ‘ant-sclective.” Ifthe activity loss is proportional to the concentration oF adsorhed raison, the poisoning is “nonselective * Poisoning mmidoice- oh “Tree kinds of pooning ures in ems of normed activi ‘cous nomad puso concen a ova. & 0. CO poisoning of part Salone el Begetet Ree sonra ff cae, Poisoning H, adsorption is f isoned sorbed Slur, 0 indeed 1, adsorption declines linearly with surur coverage, and thus it provides an courafe measure cf the unpoisoned nickel surface in Fraction! Hy Uptake partially poisoned “= fatalysis HSI,4 + Relative steady state mehanation ctiviy les for Nico, epand Ruas i fanction of gas- piso 13S + Reaction conditions: Tot KPa: $00"; 1% CC; 89% H, for Co, 2. Feand Ru; 46 CO! 9656 Hs for Ni Relative Steady-State Nethanaton Acthity (rh) 1s 30 45 60 75 90 105 Hs Concenaton, ova. | Fouling: Coking and Carbon Deposition Fouling, Coking and Carbon Deposition + Fouling is the physical (mechanical) deposition of species from the fuid phase onto the catalyst surface, which results in activity loss due to blockage of sites and/or pores. ~ Examples: mechanical deposition of earbon and. coke in porous catalysts Fouling, Coking and Carbon Deposition Metal Catal ‘Support Particle Conceptual model of fouling, crystallite encapsulation and pore lugging of supportad motl catalyst "hue to carbon deposition vm. (ara any at enyerorpey or Lay ecgette 3 met perie oe terey ‘Sry a ae De wank Uongcrin ten ‘ce es ad ‘are ag araFouling, Coking and Carbon Deposition + Carbon is a aroduct of CO dlspropotonation + Cokes produced by decomposition or condensation of| hydrocarbors on catalyst surfaces ard typically consists of polymerized heavy hydrocarbons. Fouling, Coking and Carbon Deposition £0) ec, (9010) —FEMN HC) Mechanisms of catbon formation ‘carbon monoxide [+ nee Cao) ——}—*6p 18)» ce (6) aero Fouling, Coking and Carbon Deposition Sana ~ Sate Tepeis Fens aT te TS tea Tas ane ipod area =a = ‘Mh nase es 6 am we Vonairpuetsempuarinem ten MM ‘ee sieartay 5 mw zs are é “an ne Forms and Resetivities of Carbon Species formed by Decomposition of CO on Nickel Fouling, Coking and Carbon Deposition € Gia —*atoe rie), 606.- = Cin eto ned slo) —> 6 emia aon) | Se mate) |» cys) anager an ricco) ca Sarthe cue 2a) ——*hg— he a cy) —* crate Z cles HE) —e Cy Crt) tke Ter) ays rie “Mechanisms ofan formation on metal fomfycroartonsFouling, Coking and Carbon Deposition £9 retain wae od coer cranes mencempen Lea ph Seapine” Seyetaee ince rege etnain TenentNari mine seetctnv ation Dacron SES teemgem Amp ieee oem nlc ene ilies tana Setmadtiaatenie tare coat a Kren Carbon Species Formed in Steam Reforming of Hydrocarbons on Nickel Catalysts Coke formation on oxides and sulfides ¢ + Formation of coke on oxides and sulfides is result of cenicking retinas inning eke peerrere peal alkenes or aronates) catalyzed by acid sites + Dehydrogenation and eyetization reations of earbo-cation imermediats formed on acid sites lead to aromaties, whieh react futher tohigher molecular weight paynucoa? ‘aromatics and eondense as coke Coke formation on oxides and sulfides ‘fami Aes se: Reso ane wt rma omy cae on Agta anaes Sey: Content enc enn wi 3 hae fom “Tac tached Ca scot Gih-GHCH + HE = CHER CHy a Sep: Reon xen wi id foe ane os = 9 cay t-te ht Hee —_ > .Coke formation on oxides and sulfides ou monn amino xl pe me aon esctn ines high estate ova. a ova. o-—-|d]-o-fho-o] Or Coke formation on oxides and sulfides yet Tala rena aa ae ie foam Be wn +> Wns AM (0 Tye Meghann ck seit; — SS sense ue ebm semi oys | ova. 2Thermal Degradation and Sintering Thermal Degradation and Sintering a (1) loss oFcatalstic surface area due to erytalite growth in raltie phase Sinsring) (2) loss of supper ares duc to support collapse and of catalyti surfice area due to pore collapse on metal exystllites (Sintering) (©) tansformatins of catalytic phases to noseatalytic phases. Thermal Degradation and Sintering & + Sintering processes generally take place at high reaction temperatures (above 500°C) and + Sintering processes are generally accelerated by the presence of water vapor, ‘+ Four principal Thermal Degradation and Sintering a et mechanisms of metal crystallite growth have been advanced: (1) erystalite migration, (2) atomie migraton, 6) spreading and spline, (4) (at very high temperatures) vapor transport. (8) Crystallite migrationThermal Degradation and Sintering (2) isocton and enison of etal atoms meta-onaning moles Thermal Degradation and Sintering im metal esl + In general, terrperature-induced catalyst degradation (2) stborpon td tappgof mtlatoms ar meta-consing leu processes are rapid at high reaction temperatures and the stppor sare irreversible or difficult to reverse. (dion f tl sons, metsontiing meu andor meta epi crs port ices (4) parce esting {S)suport ure wing by met pus (7) enlescence of eadeine betwen. two meal (8) cap ofan mle met piles (40) metal aor sapotzatin: and (1 tal volando ole compound osion Thermal Degradation and Sintering + Factors affecting metal particle growth and redispersion: temperature (rate increases exponentially ) atmosphere (rapidly in O, and slowly in H,) = metal type = metal dispersion ~ promoters/impurities a support surface area, texture and porosity Tent a [Normalized nickel surface area (based on Ht alsorption) versus time dala during sintering of 1339 NUSIO, in H2 at {620,700 snd 780°C, respectivelyThermal Degradation and Sintering & + Promoters or impurities affect sntering and redispersien: increasing eg. chlorine and sufi) metal atom. mobility on the suppor decreasing (e.g. oxygen. calcium. cesium) metal atom mobility on the support. Thermal Degradation and Sintering a + Sintering nite: ~d(D/DyVdt = ke(DiDy~Dea/Do)” ~ Dy: initial dispersion (percentage exposed) =D: dispersion at time" = Dag limiting dispersion — k,: sintering rate constant =m: order of sintering (is found to >e either one oF 0) me a me a Thermal Degradation and Sintering & Sintering of support a eae ea + Single-phase oxide carriers sinter by one or : ‘more ofthe following processes: Eas aa a (Usurie isin, igre, i (2) solid-state diffusion, (@) evaportion{condonsaton of wots atoms or moleces, (4) grain bcundary diffusion, Comparison of Second-Order Sintering Rate eine hares ‘Constants and Activation Encigics for Pt, Ni and Ag Catalysts Inc smote skinna andstea ee mst berm blecaters infu smote bor ae the mat hema suble ce me “ om.Sintering of support ‘+ Additives andimpurites affect the thermal properties of aire hy arcing delet sites farming new pes be spnl ses wih aia = Stam alts suger sii forning mile aise * BET whos are of of thermal teatment land chlorine content ‘fresh samples (Samples were Ireatea ar the temperature Indicated for 2) ‘Surface Areain m/e szesssss28 5 8 3 oasis Sintering of support a + Degradation of supported mmeiais by metel \Vaponization oF phase Sintering of support a + Phase transfarmations may affect the physical or chemical integrity of supported metals ‘nao enatoreaiene a ie [SE (1) reaction othe metal wit promoter andor caris, a oe epee ee insignificant rout lyst teh (3) metal and’or carrier phase transitions Sesion et ra eae cart jnyco), [48 Ty sea > ~ metattoss tough femation —[racot [= — [38 srt todd sch ‘Sites and ales con bo Sivan tate me eters orm ” ms =Sintering of support + Bx: The solid state eacton of NiO with y-AL,O; t0 forma sine ht inactive NEALO, ans alin iiing Steam-containng atmospheres at temperatires above about 400-S00°C anti. an important route for deactivation of [NIA.O, catalysts in steam reforming of methane Ex: The react of SO, with 7-A1,0, to produce ALSO), {serous eats of detctivaion in alumirasuparted atalyts for selective catalytic reduction (SCR) of nitrogen oxides (NO,) Thermal Degradation and Sintering + Effects of sintering on catalyst activity ~ for structure sensitive reactions: important for specie tivity (basco eataltic surface area) + Ex Ethane hyogenlss eta scan ening ~ forstructure insensitive reactions: no effec (in principle) specific activity * CO hyrogntion en suppor eal kel ron and ain Vapor Transport 4 Vapor Transport + The dreet volatilization of catalytic metals is generally nota factor in most catalytic processes sine the temperatires. for metal ‘vaporization exceed 1000-C (with the exception ot Hg) + stl os va formation of volte real eopounds can accra mova tmportrs (even oom tempera) Gonna mnie ape Compt GO areata RIC FAO o, oss a, ora.ROPHTO, hs ‘sti Mess")Vapor Transport a + Ex: (50%) Ru loss after testing ofa Pd-Ru catalyst nan actual elucing automobile exkaust for 100 b due to formation ofa volatile uthen um oxide. + Ex: NV/AI,O, methanation catalysts deactivate rapidly during methanation at high partial pressures of CO ( 20kPa) and temperatures below 425°C due to N(CO), formation, difusion and decomposition Vapor Transport Formation of volatile nickel tetracarbonyl atthe surface of nickel crystallite in CC atmosphere. 4 rms " me a 4 Mechanical Failure: Attrition and Crushing Generalized mechanisms and kinetis for deactivation by metal os. rms . me .Mechanical Failure: Attrition and Crushing (1) crushing of granular, pellet or monolithic catalyst forms due to a load, (2) attrition, the size reduction and/or breakup of catalyst granules or pellets “0 produce fines, especially in fluid or slurry beds, (3) erosion of catalyst particles or monolith coatings at high fluid velocities. Mechanical Failure: Attrition and Crushing + Loss ofcatalye material duc to atition caused by hersion ar eracion in mewn, ser. ne iin ee can bea serious, reversible cause of deactivation: FCC proces, Fischer-Tropsch synthesis + Aion is evident by a reduction inthe patie size ar @ rounding o smoothing ofthe catalyst patel, easily observed under an optical or electron mierscope. Mechanical Failure: Attrition and Crushing + Washeoat loson a monolith honeycomb catalyst may occur hy erinn, expevially when goers and enrind poticulaes are flowing athigh linear velocities, ander by thermally Jnduoed crack formation when rapid changes in temperature ‘eeu over many cycles ~ Gx war cri often kin ca + Washooat erosion s observed by scanningthe wal of the hhoneyeomb elannel inthe used catalyst with either an optical or elecron microscope. and its extent can be reasured by cbserving weight los over tine at high flows, Mechanical Failure: Attrition and Crushing + Crushing of catalyst pellets or monoliths may occur luc to an apalied load, c.g. catalyst et the bottom of a large packed bed may collapse due to stress exerted by the tons of eatalyst overheadMechanical Failure: Attrition and Crushing + Two principal mechanisms are involved in mechanical ‘lure of catalyst agglornerates: (1 fracture of agglomerates into smaller agglomerates of approximacly 02 d, 084, (@) Erosion of small age diameters ranging trom the agglomerate of primary particles having 1 10pm fram the surface of 2. Phuong phap phong va xt ly (Prevention and treatment) Prevention + Prevention is better than treatment + In large-scale processes, the economic retum on this investment may depend on the catalyst remaining eifective over a period of 3-5 years. &Prevention Reica Oring Ca oo Ti-neC Kamo pom Methods for Preventing Soa sete Dyan Catalyst Decay (p. 285) bras, the rte ot decaycan ten be mined by ce Crees tee cco a eta 2 Convt of pees vrs (eg tempetre, ress, nd sow rate) WIS Sewsinning ‘atv 2. Contol fedsckimpuries and methots of contacting. se . se . Prevention a Prevention é + Prevention of fouling by coke and carbon carbon or coke results from a balance between the reactions that produce atomic carbon or coke precursors and the reactions of these species with Hy H;0, or O: that remove them from the surface. {SFconditions favor formation over gasification, these specie: accumulate on the surface and react further to less active forms of carbon or coke + Prevention of fouling by coke and earbos: ‘= gasphate finmation can be minimized ty choosing reaction fen he io ot iis al (2g HEH) orgs divens and by mitring the Sod Shave avail for homogsncows rescton ~ Coke depoiton on oxie or sulie cates occus mainly fnstiongly cise accordingly the rac of coking can Pe foward y durssing ine aca fis Suppor ~ Selet econ bod or ctalyst geometries al operating cendivons hat mininize te eeu ofcoingon he * amen hy ae pw iinPrevention + Prevention of poisoning: = Removal o impure rom the few levels ha wil enable the catalystto operate atts optimum lifetime: + Ex ale compounds inconentoel melmaton and Fisher Tropeh roc molvng ert alto tan 1D ~ Lowering the rate of poisoning by careilly choosing reaction conditions, Prevention + Prevention of sintering: “Metal erste growh fa highly themally activated roves thu by chocumg rac temperres ower fan 3.03 ims the meting poi ofthe met sof etal Slnering aa be peal nized ~ voter vapor inpanicular oslerates the eysaiztion and Src madieon of xe supports mime the ~ Aang therm! stabilizes tothe sass * fica ossbr cal Ser ccl incense teal rms % rms Prevention & Basic Problem Cause + Penton oneal dealt: Mechanism c repent pea dome, Poisoning loss of catalytic blockage of sites by )aking bind 0 improve tenet and agines, the surface sites strong adsorption of Stuart ad tore Selon fam 0 impurity ove tha por bt ey f = (0) tng sans wth pr yong ns (4) chemical rina tempering of aloes to ntrodce “Method of Minimization nmpres sesses which merase reagth a ation rensonceghentne nd cooling pars rp ag og soni Mes eure frac tase the alone exon wie ekeag significant sng of or phase changes nthe porous nor (Uy purfcation of ed, guard chamber; @) elves, which selectively adsorb poison; (3) reaction conditions, which lower adsorption strength (4) mass transfer regimes, which minimize loss of activity ov.SS craeay 4 ine hselcmirnoer cae (1) restore the activity of the catalyst Sipe teen temteee geutmettrate i (regenera‘ion), a eg neon (2) use it foranother application, ee (3) reclaim and recycle the impostant and/or Soerara™™ lnc og te Onn re ‘expensive catalytic components Seen tena (4) discard the catalyst. SSS Se rma. Lilac rma. 1» Treatment a Regeneration a ‘The decision toregeneratereyele or discard the ene catalyst depende lnegely nthe rte oP deactivation I deaetvaton is very rapid, as in the coking of cracking catalysts, rested or continuous regeneraion Becomes an economic noses Disposal of caalyss containing non-nable heavy metals (€2. Cr, Pb, or Sn is environmentally problematic and should be a ast choice + The ability to reactivate a catalyst depends upon the reversibility of the deastivation process, carbon and coke formation is relatively easly reversed through gasification with hydrogen, water or oxvzen ~ Sintering, on the other hand, is generally irreversible, although metal redispesion is possible under eerain conditions in selected roble metal systems. = Some potons or fouamts ean be selectively removed by chemical washing, mechanical ueatments, heat treatments or oxidationRegeneration + Regeneration of sulfur-poisonec catalysts Ni-S+H,0 + NiO+H,S HyS+2H,0 > SO; +3Hy + Regeneration of coked catalysts: gasification with O,, HO, CO,, and Hy, ~ Relative rates of uneatalyzed asification at 10 kPa and £00°C: 0,108) > H,0(3) > CO,(1) > H,G x 10°) Regeneration + Because catalyzed removal of carbon with oxygen is gcnerally very rapid at moderate temperatures (© 5300-600°C), industrial processes typically regenerate carbon- or coke deactivated catalysts in ir ~ Catltiecackine Hygsen oencn ~ Casters me ” sme a a Regeneration é + ey issues in ar regeneration include ht spots ot cvertemperstures, which can further deactivate the catalyst. +The combusion proces is typically controled by aie 230 initially feccing low concentrations of air (+N, or Tete Ramen Pros RTC 1,0) and by increasing oxygen concentration with increasing earbon conversion (Gyeked steaming 500s hl bed Oita marae Sarin Sate ee ee Society hea mL sce Sirota ym emp ee required Ba oT ym+ Redispersion of sintered catalysts During aalytie Ringo Iydrocarbons on nl Extabagrowth ‘Syaaliter ocr = redspersion of the fi porch efor ian ‘xychionation, Regeneration ple tl lana phase bya iene Regeneration oat simospee eons ‘preter ont fal i a8 et ‘preparation nb ecesrs t- ema Dap 0) “ema Tepes C ect rhvestmat nocd) an leper ome ont dpaon a PUNO to) Pais egies e201 ara ova. 2 Deaciivation Processes ‘Modeling equations: (1) the rate equation forthe main reaction, (2) the rate equation for deactivatien, (G) the material balance or continuity equation, (the enegy balance equation. Deaciivation Processes & + Rate equations: = gery s(Cyya we i the rate of the main reactien, ~K (1) is the rate constant, =1{C)is a function of reactant and product, concentrations, nis the evectiveness factor, which accounts for effects of pre diffusional resistarce, and ~ aii the activity function or the rate of reaction on the deactivated catalyst divided by the rate on the fresh catalyst.Deactivation Processes a Deactivation rate: ny =—da/ dt = ka f(C)nsat k, is the deactivation rate constent, 1, the effectiveness factor for the deactivation process, d the order of deactivation (usually: 0-1) ym s Deaciivation Processes Sy “Table S11 ate Eatin Pair fr Diet Type of Desvan (Level 198) aon Se ectatin recerrs See ine rors apne an tnt nine AR Pelee etd pdt sn po pty ova. oye Mea Sarde at sete WCaP eet Ue Deactivation Processes u + Deactivation rates are affected by the pore diffusion + kk, and ny ny are changed when pore diffusion is considered